Who is telling you that these things have failed, and how are they justifying it, meaning what are they using as an indicator to point to a blown head gasket and faulty cat, and etc...etc...
I suppose whoever sold the truck could have weazled you, by cleaning up the engine, changing the oil, changing the coolant so it all looks clean, and if a slow leak then maybe it would have taken more than just a test drive for coolant to show up in the oil, or for oil to show up in the coolant.
It would be horrible bad luck if it passed an inspection yesterday, and then today it has blown gasket.
But for the exhaust issue..Where the exhaust pipes connect there is a seal, a leak can occur when that seal goes bad, and can have the 0420 can manifest. 17410B in the picture/link is one of the seals I'm describing. They are very cheap. Before you change out large parts of the exhaust try changing those first. When the exhaust is changed, the seal also gets changed, problem gets fixed, but what actually fixed it...1$ seal or 1000$ exhaust parts. If it doesn't work you only spent a few $ more, to test, but could be huge savings if it works.
EXHAUST PIPE. Fits: 2003 TOYOTA 4Runner SR-5 4700CC 32-VALVE DOHC EFI, AUTOMATIC 5-SPEED | Village Toyota Parts
You could also just try erasing that 0420 with an ODBII scanner and see how long it takes to come back. I think disconnecting the battery for several minutes does the same??
It might also just go away on its own, after x number of starts or miles where that error doesn't occur. I know I've cleared it, and it took many weeks of driving before it came back. And I've also had it on for a few days, before I got a chance to clear it, but then it just went away on it's own.